CN112897516A - Preparation method of graphene quantum dots - Google Patents
Preparation method of graphene quantum dots Download PDFInfo
- Publication number
- CN112897516A CN112897516A CN202110227540.3A CN202110227540A CN112897516A CN 112897516 A CN112897516 A CN 112897516A CN 202110227540 A CN202110227540 A CN 202110227540A CN 112897516 A CN112897516 A CN 112897516A
- Authority
- CN
- China
- Prior art keywords
- graphene quantum
- ball milling
- quantum dots
- mixture
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a preparation method of graphene quantum dots, which comprises the steps of placing graphite and solid melamine in a ball milling device for carrying out first ball milling treatment to obtain a ball milling mixture A; a control agent is added to the mixture a. Continuing to perform the second ball milling treatment to obtain a mixture B; and washing the ball-milling mixture B, then placing the washed ball-milling mixture B into a pretreated dialysis bag, and carrying out freeze drying treatment after the dialysis treatment is finished to obtain the graphene quantum dots. The preparation method disclosed by the invention is simple, the overall preparation process parameters are mild, the method also has the advantages of high yield of the synthesized graphene quantum dots, uniform size, high purity and high synthesis efficiency of the graphene quantum dots, and can effectively solve the problems of complex synthesis process, long synthesis time, overhigh synthesis temperature and poor environmental protection performance caused by the use of organic solvents or strong corrosive acids of the graphene quantum dots in the prior art.
Description
Technical Field
The invention relates to the field of material preparation, in particular to a preparation method of graphene quantum dots.
Background
Graphene quantum dot formed by sp2、sp3The hybridized carbon structure generally has a single-layer or multi-layer graphite structure, and the transverse size of the carbon particle is less than 20 nanometers, so that the carbon particle has special properties of good luminescence, low toxicity, solubility and the like. The graphene quantum dots containing nitrogen and oxygen-rich functional groups have high water solubility and are more compatible with biological systems, so that the preparation of the graphene quantum dots with higher quality has extremely important significance. Synthesizing the graphene quantum dots: cutting large-size graphene sheets, carbon nanotubes, carbon fibers or graphite to form nanoscale GQDs; or organic micromolecules are used as precursors to prepare GQDs by a physical and chemical method. The preparation method of the graphene quantum dot in the prior art mainly comprises a hydrothermal method, an electrochemical method, a solvothermal method, an acid oxidation method and a microwave-assisted method, but the prior art has the following problems: the synthesis process is complex, the synthesis time is long, the synthesis temperature is too high, and an organic solvent or a strong corrosive acid is used, so that the environmental protection performance is poor.
In summary, the above problems still remain to be solved in the field of graphene quantum dot preparation.
Disclosure of Invention
Based on the above, in order to solve the problems of complex graphene quantum synthesis process, long synthesis time, overhigh synthesis temperature and poor environmental protection performance in the prior art, the invention provides a preparation method of graphene quantum dots, and the specific technical scheme is as follows:
a preparation method of graphene quantum dots comprises the following steps:
placing graphite and solid melamine in a ball milling device for carrying out first ball milling treatment to obtain a ball milling mixture A;
a control agent is added to the mixture a. Continuing to perform the second ball milling treatment to obtain a mixture B;
and washing the ball-milling mixture B, then placing the washed ball-milling mixture B into a pretreated dialysis bag, and carrying out freeze drying treatment after the dialysis treatment is finished to obtain the graphene quantum dots.
Preferably, the control agent is potassium hydroxide.
Preferably, the ball milling device comprises a control device for controlling ball milling parameters.
Preferably, the ball milling parameters include a ball milling frequency and a ball milling time.
Preferably, the adding ratio of the graphite to the solid melamine to the potassium hydroxide is 1:1-3:3-9 in percentage by mass.
Preferably, the ball milling frequency is 300rpm/min to 600 rpm/min.
Preferably, the ball milling time is 3h to 24 h.
Preferably, the pretreatment is to place the dialysis bag in boiling water, and the pretreatment time is 15min-25 min.
Preferably, the dialysis treatment is performed for a period of time ranging from 1d to 5 d.
Preferably, the graphene quantum dots include nitrogen and oxygen-rich functional groups.
The preparation method of the graphene quantum dots in the scheme is simple, overall preparation process parameters are mild, the method also has the advantages of high yield of the synthesized graphene quantum dots, uniform size, high purity and high synthesis efficiency of the graphene quantum dots, and the problems of complex synthesis process, long synthesis time, overhigh synthesis temperature and poor environmental protection performance caused by the use of organic solvents or strong corrosive acids of the graphene quantum dots in the prior art can be effectively solved.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of graphene quantum dots according to the present invention;
FIG. 2 is a schematic diagram of graphene quantum dots prepared according to the present invention;
fig. 3 is a schematic transmission electron microscope, a schematic high-resolution transmission electron microscope and an atomic force microscopy of the graphene quantum dots prepared in embodiments 1 to 4, wherein fig. a is a schematic transmission electron microscope of the graphene quantum dots prepared in embodiment 1, fig. b is a schematic high-resolution transmission electron microscope of the graphene quantum dots prepared in embodiment 1, and fig. c is a schematic atomic force microscopy of the graphene quantum dots prepared in embodiment 1; fig. d is a schematic view of a transmission electron microscope of the graphene quantum dot prepared in example 2, fig. e is a schematic view of a high-resolution transmission electron microscope of the graphene quantum dot prepared in example 2, and fig. f is a schematic view of an atomic force microscope of the graphene quantum dot prepared in example 2; fig. g is a schematic view of a transmission electron microscope of the graphene quantum dot prepared in example 3, fig. h is a schematic view of a high-resolution transmission electron microscope of the graphene quantum dot prepared in example 3, and fig. i is a microscopic schematic view of an atomic force of the graphene quantum dot prepared in example 3;
FIG. 4 is a schematic diagram of X-ray photoelectron spectroscopy spectra of graphene quantum dots prepared in examples 1 to 4 of the present invention;
fig. 5 is a schematic diagram of N1s spectra of graphene quantum dots prepared in examples 1 to 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to embodiments thereof. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The preparation method of the graphene quantum dot in one embodiment of the invention comprises the following steps:
placing graphite and solid melamine in a ball milling device for carrying out first ball milling treatment to obtain a ball milling mixture A;
adding a control agent into the mixture A, and continuing to perform second ball milling treatment to obtain a mixture B;
and washing the ball-milling mixture B, then placing the washed ball-milling mixture B into a pretreated dialysis bag, and carrying out freeze drying treatment after the dialysis treatment is finished to obtain the graphene quantum dots.
The preparation method of the graphene quantum dots in the scheme is simple, overall preparation process parameters are mild, the method has the advantages of high yield of the synthesized graphene quantum dots, uniform size of the graphene quantum dots, high purity and high synthesis efficiency, and the problems of complex synthesis process, long synthesis time, overhigh synthesis temperature and poor environmental protection performance caused by the use of organic solvents or strong corrosive acids of the graphene quantum dots in the prior art can be effectively solved.
In one embodiment, the control agent is potassium hydroxide.
In one embodiment, the ball milling device comprises a control device for controlling ball milling parameters.
In one embodiment, the ball milling parameters include ball milling frequency and ball milling time.
In one embodiment, the graphite, the solid melamine and the potassium hydroxide are added in a ratio of 1:1-3:3-9 by mass percent.
In one embodiment, the ball milling frequency is 300rpm/min to 600 rpm/min.
In one embodiment, the ball milling time is 3h to 24 h.
In one embodiment, the ball milling apparatus comprises a ball milling jar.
In one embodiment, the ball mill can is internally provided with grinding balls with the diameter of 3mm-25 mm.
In one embodiment, the grinding balls are made of any one of zirconia, ceramic, polyurethane, nylon, agate, polytetrafluoroethylene and stainless steel.
In one embodiment, the pretreatment is to place the dialysis bag in boiling water, and the pretreatment time is 15min-25 min.
In one embodiment, the dialysis treatment is performed for 1d to 5 d.
In one embodiment, the graphene quantum dots include nitrogen and oxygen-rich functional groups.
In one embodiment, the graphene quantum dot is applied to preparation of a luminescent material.
Embodiments of the present invention will be described in detail below with reference to specific examples.
Example 1:
a preparation method of graphene quantum dots comprises the following specific steps:
placing 2g of graphite and 6g of melamine in a 50mL stainless steel ball milling tank by using a planetary ball mill (Nanjing Nanda instrument, QM-3SP2), loading 30 stainless steel grinding balls with the diameter of 5mm and 10 stainless steel grinding balls with the diameter of 10mm in the stainless steel ball milling tank, and carrying out ball milling for 3 hours under the condition that the ball milling frequency is 300rpm to obtain a ball milling mixture A; then adding 18g of potassium hydroxide, and continuing ball milling for 6 hours to obtain a ball-milled mixture B; washing the mixture B with 250mL of ultrapure water to remove insoluble products; and transferring the washed ball-milled mixture B into a dialysis bag pretreated in boiling water for 20min in advance, carrying out dialysis treatment for 1d to remove potassium hydroxide and melamine, and carrying out freeze drying to obtain a golden or brown solid product, thus obtaining the graphene quantum dot.
Example 2:
a preparation method of graphene quantum dots comprises the following specific steps:
placing 2g of graphite and 6g of melamine in a 50mL stainless steel ball milling tank by using a planetary ball mill (Nanjing Nanda instrument, QM-3SP2), loading 30 stainless steel grinding balls with the diameter of 5mm and 10 stainless steel grinding balls with the diameter of 10mm in the stainless steel ball milling tank, and carrying out ball milling for 3 hours under the condition that the ball milling frequency is 600rpm to obtain a ball milling mixture A; then adding 18g of potassium hydroxide, and continuing ball milling for 6 hours to obtain a ball-milled mixture B; washing the mixture B with 250mL of ultrapure water to remove insoluble products; and transferring the washed ball-milled mixture B into a dialysis bag pretreated in boiling water for 20min in advance, carrying out dialysis treatment for 1d to remove potassium hydroxide and melamine, and carrying out freeze drying to obtain a golden or brown solid product, thus obtaining the graphene quantum dot.
Example 3:
a preparation method of graphene quantum dots comprises the following specific steps:
placing 2g of graphite and 6g of melamine in a 500mL stainless steel ball milling tank by using a planetary ball mill (Nanjing Nanda instrument, QM-3SP2), loading 30 stainless steel grinding balls with the diameter of 3mm and 10 stainless steel grinding balls with the diameter of 5mm in the stainless steel ball milling tank, and carrying out ball milling for 12 hours under the condition that the ball milling frequency is 500rpm to obtain a ball milling mixture A; then adding 18g of potassium hydroxide, and continuing ball milling for 24 hours to obtain a ball-milled mixture B; washing the mixture B with 250mL of ultrapure water to remove insoluble products; and transferring the washed ball-milled mixture B into a dialysis bag pretreated in boiling water for 20min in advance, carrying out dialysis treatment for 1d to remove potassium hydroxide and melamine, and carrying out freeze drying to obtain a golden or brown solid product, thus obtaining the graphene quantum dot.
Example 4:
a preparation method of graphene quantum dots comprises the following specific steps:
placing 2g of graphite and 10g of melamine in a 500mL stainless steel ball milling tank by using a planetary ball mill (Nanjing Nanda instrument, QM-3SP2), loading 30 stainless steel grinding balls with the diameter of 3mm and 10 stainless steel grinding balls with the diameter of 5mm in the stainless steel ball milling tank, and carrying out ball milling for 3 hours under the condition that the ball milling frequency is 500rpm to obtain a ball milling mixture A; then adding 36g of potassium hydroxide, and continuing ball milling for 12 hours to obtain a ball-milled mixture B; washing the mixture B with 250mL of ultrapure water to remove insoluble products; and transferring the washed ball-milled mixture B into a dialysis bag pretreated in boiling water for 25min in advance, carrying out dialysis treatment for 3d to remove potassium hydroxide and melamine, and carrying out freeze drying to obtain a golden or brown solid product, thus obtaining the graphene quantum dot.
Comparative example 1:
a preparation method of graphene quantum dots comprises the following specific steps:
placing 2g of graphite and 6g of melamine in a 50mL stainless steel ball milling tank by using a planetary ball mill (Nanjing Nanda instrument, QM-3SP2), loading 30 stainless steel grinding balls with the diameter of 5mm and 10 stainless steel grinding balls with the diameter of 10mm in the stainless steel ball milling tank, and carrying out ball milling for 3 hours under the condition that the ball milling frequency is 300rpm to obtain a ball milling mixture A; then adding 30g of potassium hydroxide, and continuing ball milling for 6 hours to obtain a ball-milled mixture B; washing the mixture B with 250mL of ultrapure water to remove insoluble products; and transferring the washed ball-milled mixture B into a dialysis bag pretreated in boiling water for 20min in advance, carrying out dialysis treatment for 1d to remove potassium hydroxide and melamine, and carrying out freeze drying to obtain a golden or brown solid product, thus obtaining the graphene quantum dot.
Comparative example 2:
a preparation method of graphene quantum dots comprises the following specific steps:
placing 2g of graphite and 6g of melamine in a 50mL stainless steel ball milling tank by using a planetary ball mill (Nanjing Nanda instrument, QM-3SP2), loading 30 stainless steel grinding balls with the diameter of 2mm and 10 stainless steel grinding balls with the diameter of 40mm in the stainless steel ball milling tank, and carrying out ball milling for 3 hours under the condition that the ball milling frequency is 600rpm to obtain a ball milling mixture A; then adding 18g of potassium hydroxide, and continuing ball milling for 6 hours to obtain a ball-milled mixture B; washing the mixture B with 250mL of ultrapure water to remove insoluble products; and transferring the washed ball-milled mixture B into a dialysis bag pretreated in boiling water for 20min in advance, carrying out dialysis treatment for 1d to remove potassium hydroxide and melamine, and carrying out freeze drying to obtain a golden or brown solid product, thus obtaining the graphene quantum dot.
Comparative example 3:
a preparation method of graphene quantum dots comprises the following specific steps:
mechanically mixing graphite powder blocks with cesium carbonate molten salt; preheating at the temperature of 300-450 ℃ and preserving heat at the temperature of 550-650 ℃; cooling to room temperature, and soaking in water to obtain suspension; and centrifuging the suspension to obtain the graphene quantum dots.
The yields and purities of the graphene quantum dots prepared in examples 1 to 4 and comparative examples 1 to 3 are shown in table 1 below.
Table 1:
as can be seen from the data analysis in table 1, the preparation method of the graphene quantum dot of the present invention obtains a higher yield of the graphene quantum dot; the graphene quantum dots prepared in the embodiments 1 to 4 of the present invention have higher purity than the graphene quantum dots prepared in the comparative examples 1 to 3. As shown in fig. 1, the method for preparing the graphene quantum dots is simple and has strong operability; fig. 2 is a schematic diagram of a product of the graphene quantum dot prepared by the present invention, and it can be known that the graphene quantum dot prepared by the present invention has a uniform color.
In addition, the graphene quantum dots prepared in example 1 were labeled as sample N-GQDs-300, the graphene quantum dots prepared in example 2 were labeled as sample N-GQDs-600, the graphene quantum dots prepared in example 3 were labeled as sample N-GQDs-500-1, and the graphene quantum dots prepared in example 4 were labeled as sample N-GQDs-500-2. As can be seen from FIG. 3, the images a, b and c in FIG. 3 respectively show the transmission electron microscope, high resolution transmission electron microscope analysis and atomic force microscopy analysis images of the sample N-GQDs-300; FIG. 3 is a transmission electron microscope, a high resolution transmission electron microscope analysis and an atomic force microscopy analysis picture of the sample N-GQDs-600; in FIG. 3, the images g, h and i are transmission electron microscope, high resolution transmission electron microscope analysis and atomic force microscopy analysis pictures of the sample N-GQDs-500-1, respectively. Analysis of graphs a-i in fig. 3 shows that the average diameter of the graphene quantum dots prepared by the method is less than 5nm, the thickness of the graphene quantum dots is 1nm-2nm, and the graphene quantum dots are obviously uniform in size.
FIG. 4 is a schematic diagram showing X-ray photoelectron spectroscopy totals of the sample N-GQDs-300, the sample N-GQDs-600, the sample N-GQDs-500-1, and the sample N-GQDs-500-2; FIG. 5 is a schematic diagram of the spectra of N1s of sample N-GQDs-300, sample N-GQDs-600, sample N-GQDs-500-1, and sample N-GQDs-500-2, as can be seen by analysis in conjunction with FIGS. 4 and 5: the graphene quantum dot prepared by the invention is uniform in size, is rich in various oxygen functional groups of C-O, C-O, O-C-O, has excellent water solubility, and can be proved to be high in stability and free of agglomeration and sedimentation.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of graphene quantum dots is characterized by comprising the following steps:
placing graphite and solid melamine in a ball milling device for carrying out first ball milling treatment to obtain a ball milling mixture A;
adding a control agent into the mixture A, and continuing to perform second ball milling treatment to obtain a mixture B;
and washing the ball-milling mixture B, then placing the washed ball-milling mixture B into a pretreated dialysis bag, and carrying out freeze drying treatment after the dialysis treatment is finished to obtain the graphene quantum dots.
2. The method for preparing the graphene quantum dot according to claim 1, wherein the control agent is potassium hydroxide.
3. The method for preparing graphene quantum dots according to claim 1, wherein the ball milling device comprises a control device, and the control device is used for controlling ball milling parameters.
4. The method according to claim 3, wherein the ball milling parameters include a ball milling frequency and a ball milling time.
5. The preparation method of the graphene quantum dot according to claim 1, wherein the adding ratio of the graphite to the solid melamine to the potassium hydroxide is 1:1-3:5-9 by mass percent.
6. The preparation method of the graphene quantum dot according to claim 4, wherein the ball milling frequency is 300rpm/min to 600 rpm/min.
7. The preparation method of the graphene quantum dot according to claim 6, wherein the ball milling time is 3h-36 h.
8. The preparation method of the graphene quantum dot according to claim 1, wherein the pretreatment is to place the dialysis bag in boiling water, and the pretreatment time is 15min to 25 min.
9. The method for preparing graphene quantum dots according to claim 8, wherein the dialysis treatment time is 1d-5 d.
10. The method of claim 1, wherein the graphene quantum dot comprises nitrogen and oxygen-rich functional groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110227540.3A CN112897516A (en) | 2021-03-02 | 2021-03-02 | Preparation method of graphene quantum dots |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110227540.3A CN112897516A (en) | 2021-03-02 | 2021-03-02 | Preparation method of graphene quantum dots |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112897516A true CN112897516A (en) | 2021-06-04 |
Family
ID=76108528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110227540.3A Pending CN112897516A (en) | 2021-03-02 | 2021-03-02 | Preparation method of graphene quantum dots |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112897516A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113817182A (en) * | 2021-08-26 | 2021-12-21 | 四川大学 | Preparation method of high-barrier polymer-based composite material |
-
2021
- 2021-03-02 CN CN202110227540.3A patent/CN112897516A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| MAOJUN DENG等: "Graphene quantum dots: efficient mechanosynthesis, white-light and broad linear excitation-dependent photoluminescence and growth inhibition of bladder cancer cells", 《ROYAL SOCIETY OF CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113817182A (en) * | 2021-08-26 | 2021-12-21 | 四川大学 | Preparation method of high-barrier polymer-based composite material |
| CN113817182B (en) * | 2021-08-26 | 2022-06-21 | 四川大学 | Preparation method of high-barrier polymer-based composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110143586B (en) | Preparation method of single-layer or few-layer graphene | |
| EP3056469B1 (en) | Production method for graphene | |
| EP2105407B1 (en) | Continuous methods and apparatus of functionalizing carbon nanotube | |
| CN102755885B (en) | Hydrothermal preparation method of TiO2-rGO composite photochemical catalyst | |
| CN108529601B (en) | Preparation method of high-quality nitrogen-doped graphene quantum dots | |
| Fan et al. | Controlled synthesis of single-crystalline Mg (OH) 2 nanotubes and nanorods via a solvothermal process | |
| JP6979082B2 (en) | Methods for Producing Reduced Graphene Oxide from Quiche Graphite | |
| US20080105085A1 (en) | Method Of Production Of High Purity Silver Particles | |
| KR20090065205A (en) | Process for preparing graphene shell and graphene shell obtained by same process | |
| US20200048096A1 (en) | Method for preparing graphene oxide quantum dots in a large scale with cryptocrystalline graphite | |
| CN108485659B (en) | Amphiphilic graphene quantum dot material, preparation method and application of amphiphilic graphene quantum dot material as cell nucleus targeted imaging fluorescent probe | |
| KR20130137839A (en) | Manufacturing method of graphene | |
| CN112897516A (en) | Preparation method of graphene quantum dots | |
| EP3572375B1 (en) | Graphite-like microcrystal carbon nanomaterial, preparation method therefor and use thereof | |
| CN107055518B (en) | A kind of application for the method and graphene powder preparing graphene powder by crushing | |
| KR20210128176A (en) | Method for Preparing Graphene-Carbon Nanotube Composite | |
| Kobayashi et al. | Preparation of CuO nanoparticles by metal salt-base reaction in aqueous solution and their metallic bonding property | |
| CN111662547A (en) | Molybdenum disulfide quantum dot/graphene/polymer-based super-wear-resistant self-lubricating composite material and preparation method and application thereof | |
| KR102072914B1 (en) | A method for eco-friendly production of oxidized graphite and oxidized graphene using a hydroxylation reaction | |
| CN106001610A (en) | Preparation method of silver nanowire | |
| KR101737027B1 (en) | Dispersion of Graphene Oxide and Fabrication Method Thereof | |
| CN112218825A (en) | Method for producing graphene oxide from crystalline graphite | |
| CN1176847C (en) | Process for preparing titanium diboride nano powder | |
| CN113751707A (en) | Method for preparing nano carbide particle dispersion strengthening alloy powder | |
| KR101670662B1 (en) | Fabrication Method of Graphene Oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210604 |
|
| RJ01 | Rejection of invention patent application after publication |